CN116904192A - Preparation method and application of all-inorganic perovskite quantum dot - Google Patents
Preparation method and application of all-inorganic perovskite quantum dot Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 10
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- 239000002243 precursor Substances 0.000 claims abstract description 35
- 239000002904 solvent Substances 0.000 claims abstract description 28
- MBHINSULENHCMF-UHFFFAOYSA-N n,n-dimethylpropanamide Chemical compound CCC(=O)N(C)C MBHINSULENHCMF-UHFFFAOYSA-N 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 claims abstract description 15
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- GRHQDJDRGZFIPO-UHFFFAOYSA-N 4-bromobutanoic acid Chemical compound OC(=O)CCCBr GRHQDJDRGZFIPO-UHFFFAOYSA-N 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 5
- WNXNUPJZWYOKMW-UHFFFAOYSA-N 5-bromopentanoic acid Chemical compound OC(=O)CCCCBr WNXNUPJZWYOKMW-UHFFFAOYSA-N 0.000 claims description 4
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- IHCCLXNEEPMSIO-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperidin-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1CCN(CC1)CC(=O)N1CC2=C(CC1)NN=N2 IHCCLXNEEPMSIO-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
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- SXAMGRAIZSSWIH-UHFFFAOYSA-N 2-[3-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-1,2,4-oxadiazol-5-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1=NOC(=N1)CC(=O)N1CC2=C(CC1)NN=N2 SXAMGRAIZSSWIH-UHFFFAOYSA-N 0.000 description 1
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- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical class O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/66—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing germanium, tin or lead
- C09K11/664—Halogenides
- C09K11/665—Halogenides with alkali or alkaline earth metals
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y20/00—Nanooptics, e.g. quantum optics or photonic crystals
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- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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Abstract
The application relates to a preparation method and application of an all-inorganic perovskite quantum dot, wherein the preparation method comprises the following steps: the molar ratio is 1.8-2.2: 1.8 to 2.2:0.9 to 1.1: pbX of 0.9-3.3 2 Dissolving CsX, bromoacid and oleylamine into a predetermined solvent to obtain a premix; reacting the premix at a first temperature to obtain a precursor solution; adding the precursor solution into hot water at a second temperature for reaction, then carrying out solid-liquid separation, and collecting clear liquid to obtain CsPbX 3 And the predetermined solvent is a mixed solvent of N, N-dimethylacetamide and N, N-dimethylpropionamide. The application can increase CsPbX 3 Quantum yield of quantum dots, reduced defects, and improved luminous intensity.
Description
Technical Field
The application relates to the field of quantum dots, in particular to perovskite quantum dots.
Background
The perovskite quantum dots have been rapidly developed in the fields of photovoltaics, light-emitting diodes, detectors, lasers and the like due to excellent performances such as high light absorption coefficient, precisely adjustable band gap, long carrier diffusion length, high quantum yield, pure emission spectrum and the like. Wherein the inorganic perovskite quantum dot CsPbX 3 (x=cl, br, I), a fluorescent nanomaterial with a surface coated with hydrophobic ligands. In theory, the photoelectric property of the fluorescent dye is excellent, such as good stability and biocompatibility; higher fluorescence quantum yield (-90%); narrower emission peaks (half-width 12-42 nm); the emission spectrum covers the whole visible wavelength (410-700 nm); the emission wavelength is continuously adjustable; the crystal phase can change with the difference of the synthesis temperature and the halogen element contained in the molecular formula. But CsPbX synthesized in the prior art 3 Perovskite quantum dots are sensitive to water, have low quantum yields, are more defective and have weak luminous intensity, severely hampering their practical application.
Disclosure of Invention
The embodiment of the application provides a preparation method of an all-inorganic perovskite quantum dot, which aims to solve the problem of CsPbX synthesized in the prior art 3 The perovskite quantum dots have the technical problems of sensitivity to water, low quantum yield, more defects and weak luminous intensity.
In a first aspect, an embodiment of the present application provides a method for preparing all-inorganic perovskite quantum dots, where the method for preparing all-inorganic perovskite quantum dots includes the following steps:
the molar ratio is 1.8-2.2: 1.8 to 2.2:0.9 to 1.1: pbX of 0.9-3.3 2 Dissolving CsX, bromoacid and oleylamine into a predetermined solvent to obtain a premix;
reacting the premix at a first temperature to obtain a precursor solution;
adding the precursor solution into hot water at a second temperature for reaction, then carrying out solid-liquid separation, and collecting clear liquid to obtain CsPbX 3 An aqueous solution of perovskite quantum dots,
wherein, X is one of Cl, br or I,
the predetermined solvent is a mixed solvent of N, N-dimethylacetamide and N, N-dimethylpropionamide.
In some embodiments of the application, the volume ratio of N, N-dimethylacetamide to N, N-dimethylpropionamide is 1:0.25 to 1.5.
In some embodiments of the application, the volume ratio of N, N-dimethylacetamide to N, N-dimethylpropionamide is 1:0.66 to 1.5.
In some embodiments of the application, the molar ratio will be 1.8 to 2.2:1.8 to 2.2:0.9 to 1.1: pbX of 0.9-3.3 2 Dissolving CsX bromoacid and oleylamine in a predetermined solvent, wherein 0.18-0.22 mmol PbX is dissolved in each 5mL of the predetermined solvent 2 0.18 to 0.22mmol CsX, 0.9 to 1.1mmol bromoacid and 0.9 to 3.3mmol oleylamine.
In some embodiments of the present application, the precursor solution is added to hot water at the second temperature to perform the reaction, and the volume ratio of the precursor solution to the hot water is 1:10-1:16.
In some embodiments of the application, the first temperature is 55 to 65 ℃.
In some embodiments of the application, the second temperature is 55-65 ℃.
In some embodiments of the application, the bromoacid is at least one of 3-bromopropionic acid, 4-bromobutyric acid, or 5-bromopentanoic acid.
In a second aspect, an embodiment of the present application provides an application of an all-inorganic perovskite quantum dot, where the perovskite quantum dot is a perovskite quantum dot prepared by any one of the embodiments of the first aspect, and the perovskite quantum dot is applied to a luminescent material.
Compared with the prior art, the technical scheme provided by the embodiment of the application has the following advantages:
according to the preparation method of the all-inorganic perovskite quantum dot, provided by the embodiment of the application, the mixed solvent of N, N-Dimethylacetamide (DMA) and N, N-Dimethylpropionamide (DMPA) in a specific proportion is used, so that the number of the Guttman donors in a solvent system can be reduced, and zwitterionic ligands are generated by the reaction of bromoacid and oleylamine to further stabilize Cs 4 PbBr 6 Crystals, so that small-sized Cs with fewer grown defect states are produced in the solvent 4 PbBr 6 And (5) a crystal. Due to CsPbX 3 Perovskite quantum dots are Cs 4 PbBr 6 The crystal generates phase change in water and inherits Cs to a great extent 4 PbBr 6 Better crystal quality of the crystal, thereby increasing CsPbX 3 Quantum yield of the quantum dots, defect reduction and luminous intensity improvement. In addition, the method provided by the application can be carried out under the general process condition, and the used N, N-dimethyl propionamide (DMPA) has low price, small use amount and low cost.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments consistent with the application and together with the description, serve to explain the principles of the application.
In order to more clearly illustrate the embodiments of the application or the technical solutions of the prior art, the drawings which are used in the description of the embodiments or the prior art will be briefly described, and it will be obvious to a person skilled in the art that other drawings can be obtained from these drawings without inventive effort.
FIG. 1 is a schematic flow chart of a method for preparing an all-inorganic perovskite quantum dot according to an embodiment of the application;
FIG. 2 shows CsPbI in examples 1-3 of the application 3 PL spectra of quantum dot materials;
FIG. 3 is CsPbBr in examples 4-7 and comparative examples 1-2 of the present application 3 PL spectra of quantum dot materials;
FIG. 4 shows Cs in example 4 and comparative example 1 of the present application 4 PbBr 6 Cs of precursor solution 4 PbBr 6 XRD spectrum corresponding to crystal precipitation;
FIG. 5 shows Cs in example 4 of the present application 4 PbBr 6 Cs of precursor solution 4 PbBr 6 SEM image of crystal precipitation;
FIG. 6 shows Cs in comparative example 1 of the present application 4 PbBr 6 Cs of precursor solution 4 PbBr 6 SEM image of crystal precipitation;
FIG. 7 shows CsPbI in example 1 of the present application 3 TEM image of quantum dot material;
FIG. 8 is CsPbBr in example 4 of the present application 3 A TEM image of the quantum dot material.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present application more apparent, the technical solutions of the embodiments of the present application will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present application, and it is apparent that the described embodiments are some embodiments of the present application, but not all embodiments of the present application. All other embodiments, which can be made by those skilled in the art based on the embodiments of the application without making any inventive effort, are intended to be within the scope of the application.
Unless specifically stated otherwise, the terms used herein should be understood as meaning as commonly used in the art. Accordingly, unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. In case of conflict, the present specification will control.
Unless otherwise specifically indicated, the various raw materials, reagents, instruments, equipment and the like used in the present application are commercially available or may be prepared by existing methods.
CsPbX synthesized in the prior art 3 Perovskite quantum dots have the technical problems of low quantum yield, more defects and weak luminous intensity.
The technical scheme provided by the embodiment of the application aims to solve the technical problems, and the overall thought is as follows:
in a first aspect, an embodiment of the present application provides a method for preparing all-inorganic perovskite quantum dots, where the method for preparing all-inorganic perovskite quantum dots includes the following steps:
s1: the molar ratio is 1.8-2.2: 1.8 to 2.2:0.9 to 1.1: pbX of 0.9-3.3 2 Dissolving the brominated acid and the oleylamine into a preset solvent to obtain a premix;
s2: reacting the premix at a first temperature to obtain a precursor solution;
s3: adding the precursor solution into hot water at a second temperature for reaction, then carrying out solid-liquid separation, and collecting clear liquid to obtain CsPbX 3 An aqueous solution of perovskite quantum dots,
wherein, X is one of Cl, br or I,
the predetermined solvent is a mixed solvent of N, N-dimethylacetamide and N, N-dimethylpropionamide.
Solid-liquid separation is a conventional means in the art. Centrifugation may be preferred in the present application.
The precursor solution of the present application contains a large amount of Cs 4 PbBr 6 And (5) a crystal. CsPbX in the application 3 Perovskite quantum dots are formed by Cs 4 PbBr 6 The crystal is obtained through phase transformation.
Current sum CsPbX 3 In perovskite quantum dot-related work, no mention is made of Cs 4 PbBr 6 The presence of crystals and their use with CsPbX 3 Relationship of perovskite quantum dots. The inventors of the present application found that, at least in the present application, csPbX 3 Perovskite quantum dots are Cs 4 PbBr 6 The phase change of the crystal in water occurs, thus CsPbX 3 Crystal quality of perovskite quantum dot and Cs in precursor solution 4 PbBr 6 The quality of the crystals has a positive correlation.
In Pb-containing 2+ In the preparation of perovskite quantum dots, the number of the Guttman Donor (DN) can be estimated for Pb of the solvent and the lead halide precursor 2+ Coordination ability of the center. Solvent and Pb with higher Guttman donor number 2+ The more the coordination capacity of the center is, the more the halide coordination is inhibited and the perovskite crystallization is hindered. Conversely, low-Guttman donor number solublesThe agent is favorable for Pb 2+ Complex with halides and promote crystallization of perovskite. The number of the Gottman donor in the perovskite precursor liquid solvent can be effectively changed by adjusting the number of the Gottman donor in the perovskite precursor liquid solvent 4 PbBr 6 Crystallinity of the crystal, thereby reducing Cs 4 PbBr 6 CsPbX produced by phase change of crystals in water 3 Defective state of perovskite quantum dot, and improvement of water stability CsPbX 3 The luminous intensity of the quantum dots.
The precursor solution is present in a substantial amount of zwitterionic ligands. These zwitterionic ligands are generated by the reaction of bromoacid with oleylamine in a solvent, and they are located in Cs 4 PbBr 6 The surface of the crystal can reduce Cs 4 PbBr 6 Defects in the crystal, on the one hand, contribute to an increase in Cs 4 PbBr 6 The quality of the crystals, on the other hand, is beneficial to increasing the small-size Cs 4 PbBr 6 Stability of the crystals in the solvent.
The application can reduce the number of the Gutman donors in a solvent system by using the mixed solvent of N, N-Dimethylacetamide (DMA) and N, N-Dimethylpropionamide (DMPA) in a specific proportion, and further stabilize Cs by generating amphoteric ligand through the reaction of bromoacid and oleylamine 4 PbBr 6 Crystals, so that small-sized Cs with fewer grown defect states are produced in the solvent 4 PbBr 6 And (5) a crystal. Due to CsPbX 3 Perovskite quantum dots are Cs 4 PbBr 6 The crystal generates phase change in water and inherits Cs to a great extent 4 PbBr 6 Better crystal quality of the crystal, thereby increasing CsPbX 3 Quantum yield of the quantum dots, defect reduction and luminous intensity improvement. In addition, the method provided by the application can be carried out under the general process condition, and the used N, N-dimethyl propionamide (DMPA) has low price, small use amount and low cost.
In some embodiments of the application, the volume ratio of N, N-dimethylacetamide to N, N-dimethylpropionamide is 1:0.25 to 1.5.
The predetermined solvent configured by the above ratio is advantageous in reducing the number of the guttmann donors.
In some embodiments of the application, the volume ratio of N, N-dimethylacetamide to N, N-dimethylpropionamide is 1:0.66 to 1.5.
The predetermined solvent configured by the above ratio is advantageous in further reducing the number of the guttmann donors.
In some embodiments of the application, the molar ratio will be 1.8 to 2.2:1.8 to 2.2:0.9 to 1.1: pbX of 0.9-3.3 2 Dissolving CsX bromoacid and oleylamine in a predetermined solvent, wherein 0.18-0.22 mmol PbX is dissolved in each 5mL of the predetermined solvent 2 0.18 to 0.22mmol CsX, 0.9 to 1.1mmol bromoacid and 0.9 to 3.3mmol oleylamine.
The dosage of the raw materials is favorable for maintaining Cs in the precursor solution 4 PbBr 6 Concentration of crystals and at the same time maintain Cs 4 PbBr 6 The stability of the crystal and the agglomeration phenomenon are less generated.
In some embodiments of the present application, the precursor solution is added to hot water at the second temperature to perform the reaction, and the volume ratio of the precursor solution to the hot water is 1:10-1:16.
Controlling the volume ratio of the precursor solution and the hot water to be CsPbX in the above range 3 The quantum dots provide larger dispersion space, and simultaneously control the water consumption, control the total volume of the reaction system and facilitate the subsequent operation.
In some embodiments of the application, the first temperature is 55 to 65 ℃.
In some embodiments of the application, the second temperature is 55-65 ℃.
Cs generated at above temperature 4 PbBr 6 Crystal and CsPbX 3 The quantum dots have higher quality and can maintain a faster generation rate.
In some embodiments of the application, the bromoacid is at least one of 3-bromopropionic acid, 4-bromobutyric acid, or 5-bromopentanoic acid.
In a second aspect, an embodiment of the present application provides an application of an all-inorganic perovskite quantum dot, where the perovskite quantum dot is a perovskite quantum dot prepared by any one of the embodiments of the first aspect, and the perovskite quantum dot is applied to a luminescent material.
The application will be further illustrated with reference to specific examples. It is to be understood that these examples are illustrative of the present application and are not intended to limit the scope of the present application. The experimental procedures, which are not specified in the following examples, are generally determined according to national standards. If the corresponding national standard does not exist, the method is carried out according to the general international standard, the conventional condition or the condition recommended by the manufacturer.
Example 1
In this embodiment, a CsPbI is provided 3 The preparation method of the perovskite quantum dot solution comprises the following steps:
will be 0.2mmol PbI 2 0.2mmol CsI, 1mmol 3-bromopropionic acid, 1mmol oleylamine, 3mL N, N-Dimethylacetamide (DMA) and 2mL N, N-Dimethylpropionamide (DMPA) were added to a reaction flask to obtain a mixed solution, and the mixed solution was sufficiently stirred at 60℃for 10 hours to prepare a desired zwitterionic ligand and Cs in a large amount 4 PbBr 6 A precursor solution of the crystals, which is a yellow turbid solution containing a large amount of white precipitate;
the precursor solution was shaken well before use, then 180. Mu.L of the precursor solution was added to 2.5mL of deionized water at 60℃with continuous magnetic stirring, centrifuged at 4000rpm for 8 minutes, and the supernatant was taken to give CsPbI 3 Perovskite quantum dot aqueous solution.
Example 2
This example differs from example 1 only in that 3-bromopropionic acid in step (1) was replaced with 4-bromobutyric acid.
Example 3
This example differs from example 1 only in that 3-bromopropionic acid in step (1) was replaced with 5-bromopentanoic acid.
Example 4
In this embodiment a CsPbBr is provided 3 The preparation method of the perovskite quantum dot solution comprises the following steps:
will be 0.2mmol PbBr 2 0.2mmol CsBr, 1mmol 4-bromopropionic acid, 1mmol oleylamine, 3mL N, N-Dimethylacetamide (DMA) and 2mL NAdding N-dimethyl propionamide (DMPA) into a reaction bottle to obtain a mixed solution, and stirring the mixed solution at 60 ℃ for 10 hours to obtain the required compound with a large amount of zwitterionic ligands and Cs 4 PbBr 6 A precursor solution of the crystals, which is a white turbid solution containing a large amount of white precipitate;
the precursor solution was shaken well before use, then 180. Mu.L of the precursor solution was added to 2.5mL of deionized water at 60℃with continuous magnetic stirring, centrifuged at 4000rpm for 8 minutes, and the supernatant was taken to give CsPbBr 3 Perovskite quantum dot aqueous solution.
Example 5
This example differs from example 4 only in that 3mL of N, N-Dimethylacetamide (DMA) and 2mL of N, N-Dimethylpropionamide (DMPA) in step (1) were replaced with 4mL of N, N-Dimethylacetamide (DMA) and 1mL of N, N-Dimethylpropionamide (DMPA).
Example 6
This example differs from example 4 only in that 3mL of N, N-Dimethylacetamide (DMA) and 2mL of N, N-Dimethylpropionamide (DMPA) in step (1) were replaced with 2mL of N, N-Dimethylacetamide (DMA) and 3mL of N, N-Dimethylpropionamide (DMPA).
Example 7
This example differs from example 4 only in that 3mL of N, N-Dimethylacetamide (DMA) and 2mL of N, N-Dimethylpropionamide (DMPA) in step (1) were replaced with 1mL of N, N-Dimethylacetamide (DMA) and 4mL of N, N-Dimethylpropionamide (DMPA).
Comparative example 1
This comparative example differs from example 4 only in that 3mL of N, N-Dimethylacetamide (DMA) and 2mL of N, N-Dimethylpropionamide (DMPA) in step (1) were replaced with 5mL of N, N-Dimethylacetamide (DMA).
Comparative example 2
This comparative example differs from example 4 only in that 3mL of N, N-Dimethylacetamide (DMA) and 2mL of N, N-Dimethylpropionamide (DMPA) in step (1) were replaced with 5mL of N, N-Dimethylpropionamide (DMPA).
Related experiment and effect data:
FIG. 2 is CsPbI in examples 1-3 of the application 3 PL spectra corresponding to quantum dot materials. As can be seen from fig. 2, example 2 > example 3 > example 1, in terms of luminous intensity. This indicates that 4-bromobutyric acid is a preferred reagent.
FIG. 3 is CsPbBr in examples 4-7, comparative examples 1-2 of the present application 3 PL spectrum of quantum dot material.
Examples 4-7 and comparative examples 1-2 differ in the volumetric proportions of the two solvents used for DMA and DMPA. The statistics are as follows:
| volume ratio of DMA to DMPA | |
| Comparative example 1 | 5:0 |
| Example 5 | 4:1 |
| Example 4 | 3:2 |
| Example 6 | 2:3 |
| Example 7 | 1:4 |
| Comparative example 2 | 0:5 |
As can be seen from fig. 3, the light emission intensity of example 4 is highest among examples 4 to 7 and comparative examples 1 to 2, which indicates that the ratio of DMA to DMPA by volume of 3:2 achieves the best effect, and deviation from this ratio results in a decrease in light emission intensity.
Taking the precursor solutions in the example 4 and the comparative example 1, standing and drying to obtain Cs 4 PbBr 6 Depositing crystals and taking the Cs 4 PbBr 6 The crystal precipitate was subjected to XRD testing. FIG. 4 shows Cs in example 4 and comparative example 1 of the present application 4 PbBr 6 Cs of precursor solution 4 PbBr 6 XRD patterns corresponding to crystal precipitation. As can be seen from fig. 4, DMPA was used in example 4 compared to comparative example 1, which uses only DMA single solvent: cs after DMPA mixed solvent 4 PbBr 6 The crystal precipitate has more excellent crystallinity, and particularly has stronger diffraction peaks at 12 ° and 25 °.
Taking the precursor solutions in the example 4 and the comparative example 1, standing and drying to obtain Cs 4 PbBr 6 Depositing crystals and taking the Cs 4 PbBr 6 The crystal precipitate was subjected to SEM testing. FIGS. 5 and 6 show Cs in example 4 and comparative example 1, respectively, of the present application 4 PbBr 6 Cs of precursor solution 4 PbBr 6 SEM image corresponding to crystal precipitation. With the aggregated Cs obtained in comparative example 1 in FIG. 6 4 PbBr 6 As compared to the polycrystalline thin film, it can be seen from fig. 5 that DMPA is used in example 4: cs after DMPA mixed solvent 4 PbBr 6 The crystals contained more individual small crystal particles with a distinct regular shape and crystal orientation, indicating Cs 4 PbBr 6 The crystal precipitate has more excellent crystallinity.
CsPbI in example 1 3 Quantum dots and CsPbBr in example 4 3 TEM detection of quantum dot material shows the results in FIG. 7 and FIG. 8, and CsPbI can be seen from the graphs 3 Quantum dot and CsPbBr 3 Quantum dots all exhibit uniform size.
Various embodiments of the application may exist in a range of forms; it should be understood that the description in a range format is merely for convenience and brevity and should not be construed as a rigid limitation on the scope of the application; it is therefore to be understood that the range description has specifically disclosed all possible sub-ranges and individual values within that range. For example, it should be considered that a description of a range from 1 to 6 has specifically disclosed sub-ranges, such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6, etc., as well as single numbers within the range, such as 1, 2, 3, 4, 5, and 6, wherever applicable. In addition, whenever a numerical range is referred to herein, it is meant to include any reference number (fractional or integer) within the indicated range.
In the present application, unless otherwise specified, terms such as "upper" and "lower" are used specifically to refer to the orientation of the drawing in the figures. In addition, in the description of the present specification, the terms "include", "comprising" and the like mean "including but not limited to". Moreover, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising … …" does not exclude the presence of other like elements in a process, method, article or apparatus that comprises the element. Relational terms such as "first" and "second", and the like may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Herein, "and/or" describing an association relationship of an association object means that there may be three relationships, for example, a and/or B, may mean: a alone, a and B together, and B alone. For the association relation of more than three association objects described by the "and/or", it means that any one of the three association objects may exist alone or any at least two of the three association objects exist simultaneously, for example, for a, and/or B, and/or C, any one of the A, B, C items may exist alone or any two of the A, B, C items exist simultaneously or three of the three items exist simultaneously. Herein, "at least one" means one or more, and "a plurality" means two or more. "at least one", "at least one" or the like refer to any combination of these items, including any combination of single item(s) or plural items(s). For example, "at least one (individual) of a, b, or c," or "at least one (individual) of a, b, and c," may each represent: a, b, c, a-b (i.e., a and b), a-c, b-c, or a-b-c, wherein a, b, c may be single or multiple, respectively.
The foregoing is only a specific embodiment of the application to enable those skilled in the art to understand or practice the application. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the application. Thus, the present application is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (9)
1. The preparation method of the all-inorganic perovskite quantum dot is characterized by comprising the following steps of:
the molar ratio is 1.8-2.2: 1.8 to 2.2:0.9 to 1.1: pbX of 0.9-3.3 2 Dissolving CsX, bromoacid and oleylamine into a predetermined solvent to obtain a premix;
reacting the premix at a first temperature to obtain a precursor solution;
adding the precursor solution into hot water at a second temperature for reaction, then carrying out solid-liquid separation, and collecting clear liquid to obtain CsPbX 3 Perovskite quantum dot aqueous solution;
wherein, X is one of Cl, br or I;
the predetermined solvent is a mixed solvent of N, N-dimethylacetamide and N, N-dimethylpropionamide.
2. The method for preparing all-inorganic perovskite quantum dots according to claim 1, wherein the volume ratio of the N, N-dimethylacetamide to the N, N-dimethylpropionamide is 1:0.25 to 1.5.
3. The method for preparing all-inorganic perovskite quantum dots according to claim 2, wherein the volume ratio of the N, N-dimethylacetamide to the N, N-dimethylpropionamide is 1:0.66 to 1.5.
4. The method for preparing all-inorganic perovskite quantum dots according to claim 1, wherein the molar ratio is 1.8-2.2: 1.8 to 2.2:0.9 to 1.1: pbX of 0.9-3.3 2 Dissolving CsX bromoacid and oleylamine in a predetermined solvent, wherein 0.18-0.22 mmol PbX is dissolved in each 5mL of the predetermined solvent 2 0.18 to 0.22mmol CsX, 0.9 to 1.1mmol bromoacid and 0.9 to 3.3mmol oleylamine.
5. The method for preparing all-inorganic perovskite quantum dots according to claim 4, wherein the precursor solution is added into hot water at the second temperature for reaction, and the volume ratio of the precursor solution to the hot water is 1:10-1:16.
6. The method for preparing all-inorganic perovskite quantum dots according to claim 1, wherein the first temperature is 55-65 ℃.
7. The method for preparing all-inorganic perovskite quantum dots according to claim 1, wherein the second temperature is 55-65 ℃.
8. The method for preparing all-inorganic perovskite quantum dots according to claim 1, wherein the bromoacid is at least one of 3-bromopropionic acid, 4-bromobutyric acid or 5-bromopentanoic acid.
9. The application of the all-inorganic perovskite quantum dot is characterized in that the perovskite quantum dot is prepared according to any one of claims 1-8, and the perovskite quantum dot is applied to luminescent materials.
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